DE69819584T2 - Positive working lithographic printing plate - Google Patents

Description

AREA OF INVENTION

The present invention relates a photosensitive lithographic printing plate. More specifically a positive-working photosensitive lithographic printing plate.

BACKGROUND THE INVENTION

Widespread positive working Photosensitive lithographic printing plates comprise an aluminum substrate with thereon a positive-working photosensitive layer containing an o-quinone diazide compound wherein the aluminum substrate is surface graining, alkaline etching or Anodizing was subjected. The o-quinone diazide compound can be in a corresponding carboxylic acid by irradiation with ultraviolet light (hereinafter, for convenience as "UV") convert. After UV irradiation, the photosensitive layer is coated with a aqueous alkaline solution only in the UV-irradiated area to expose the substrate replaced, the fate of the lipophilic photosensitive layer in the non-irradiated area for forming an ink-receiving image surface. The UV-irradiated area (non-image area), where a hydrophilic (water-wettable) surface of the substrate exposed will, hold Water back for providing an ink-repellent surface.

Since the aluminum substrate surface a inadequate Water wettability, d. H. Ink rejection, sticks printing ink to dyeing the non-image area. To the dyeing resistance of the aluminum substrate, it is usually necessary to Non-surface water wettable close. If a substrate is made water wettable before provided a positive-working photosensitive layer thereon becomes, the resulting pressure plate is a reduced press life (the number of available satisfactory impressions) due to poor adhesion between the hydrophilic substrate and the lipophilic photosensitive Layer. Therefore, the general practice was merely the non-image area through Use of a developer containing a silicate such as sodium silicate or potassium silicate while make the plate development water wettable.

However, the silicate-containing developer precipitates SiO ₂ -derived solids, or the waste material of the developer forms gel derived from neutralizing SiO ₂ . As a result, solid matter mainly comprising silicates formed in a developing vessel or tubes of an automatic developing machine tends to cause an incorrect operation of a sensor or clog the tubes. It has therefore been demanded to develop a method of providing a positive-working photosensitive layer on a substrate which has been previously made water-wettable with good adhesion, thereby producing a printing plate having a satisfactory printing life.

To overcome problems described above, suggests US 3,136,636 the provision of an intermediate layer of a water-soluble polymer such as polyacrylic acid or carboxymethylhydroxyethyl cellulose, but the printing capacity (printing life) of the resulting plate is still unsatisfactory. US 4,483,913 discloses the provision of an intermediate layer comprising a quaternary ammonium compound such as poly (dimethyldiallylammonium chloride) but the resulting plate is unsatisfactory due to insufficient stain resistance.

It was also highlighted a positive-working lithographic printing plate precursor comprising a substrate which has been rendered water-wettable, and a positive-working photosensitive layer insufficient destruction properties owns (simplicity in destroying the unnecessary scene with a so-called destructive liquid after development), and improvement in this regard has been desired. Further the plate precursor suffers from residual color (the phenomenon that in the photosensitive layer on the existing dyes Substrate in the non-image area after Development remain) or tends to insufficient copy characteristics (the ability, a difference in optical density between an unexposed surface and an exposed area to provide development) and improvement in these respects were also welcome.

SUMMARY THE INVENTION

An object of the present invention is the provision of a positive-working photosensitive lithographic printing plate with improved stain resistance and improved press life.

Another object of the invention is the provision of a positive-working photosensitive lithographic printing plate satisfactory in its destructive properties, Freedom of remaining color, printing properties and chemical resistance (expressed through the number of satisfactory impressions obtained by Printing by wiping the image surfaces with a plate cleaner) is.

Another object of the invention is the provision of a positive-working photosensitive lithographic printing plate satisfactory in stain resistance, Press life, destruction properties, Freedom of remaining color, impression characteristics and chemical Stability even when the precursor thereof with a non-silicate developer is developed.

As a result of extensive studies The inventors have found out that the above tasks are by a positive-working photosensitive lithographic printing plate according to claim 1 to be accomplished.

In conventional processes, a printing plate prepared by forming a photosensitive layer on an aluminum substrate which has been rendered water-wettable by treatment with e.g. As a silicate, a considerably shorter press life due to poor adhesion between the water-wettable aluminum substrate and the photosensitive layer. In accordance with the present invention, improved adhesion in the image area is exerted, resulting in considerably improved press life and chemical resistance, by providing an intermediate layer containing the above-described specific polymer. Since the polymer has an affinity for an alkaline developer, the polymer of the non-image area is easily removed from the substrate by development treatment to expose the water-wettable surface of the substrate, so that the resulting plate shows satisfactory stain resistance. Since a developing solution containing a silicate is not always needed, the problems due to SiO ₂ (incorrect operation of sensors or clogging of tubes due to solid matter, mainly silicates) are eliminated and the need for such lengthy operations as cleaning or replacement, is excluded. In addition, the plate precursor surprisingly shows satisfactory post-exposure copying properties and particularly satisfactory destruction properties and freedom from residual color after development.

DETAILED DESCRIPTION OF THE INVENTION

The polymer in the intermediate layer can be used, (A) comprises a unit containing an aluminum oxide layer interacts (hereinafter referred to as "unit A ") and (B) a unit that interacts with a water-wettable layer (hereinafter referred to as "unit B ").

Unit A, with an aluminum oxide layer interacts, is a unit obtained from a monomer with a Rf value of not more than 0.5, and preferably not more than 0.2 in thin layer chromatography (DSC) mainly using a stationary phase Alumina and methanol as the developing solution and those with the following Copolymerize monomer to provide a polymer (hereinafter referred to as "monomer A "). Unit B, which interacts with a water-wettable layer, is a unit obtained from a monomer represented by Formula (III), (IV) or (V) (indicated later) with an Rf value of not more than 0.5, and preferably not more than 0.2 in DSC using a stationary phase mainly comprising silica and methanol as the developing solution and which can copolymerize with monomer A to form a polymer (hereinafter referred to as "monomer B ").

The polymer preferably closes An: addition polymers of vinyl monomers such as acrylic resins, methacrylic resins and polystyrene, or polyaddition polymers or polycondensation polymers, such as urethane resins, polyester and polyamide. Addition polymers of Vinyl monomers are preferred.

More preferred are those obtained by copolymerizing monomer A represented by formula (I) or (II) (later ) Indicated.

Monomer A is selected from a monomer with an acid radical, a monomer having an alkyleneoxy group, a monomer having a Onium group, etc.

The acid radical in monomer A preferably includes one having an acid dissociation constant (pKa) of not more than 7, more preferably -COOH, SO ₃ H, -OSO ₃ H, -PO ₃ H ₂ , -OPO ₃ H ₂ , -CONHSO ₂ - and, -SO ₂ NHSO ₂ -, more preferably -COOH.

worin A eine divalente Verknüpfungsgruppe darstellt; B eine aromatische Gruppe oder eine substituierte aromatische Gruppe darstellt; D und E jeweils eine divalente Verknüpfungsgruppe darstellen; G eine trivalente Verknüpfungsgruppe darstellt; X und X' jeweils ein Säureradikal mit einem pKa von 7 oder weniger oder ein Alkalimetall- oder Ammoniumsalz davon darstellen; R₁ ein Wasserstoffatom, eine Alkylgruppe oder ein Halogenatom darstellt; a, b, d und e jeweils 0 oder 1 darstellen; und t eine ganze Zahl von 1 bis 3 darstellt.Particularly preferred monomer A with such an acid radical is represented by formula (I) or (II):

wherein A represents a divalent linking group; B represents an aromatic group or a substituted aromatic group; D and E each represent a divalent linking group; G represents a trivalent linking group; X and X 'each represents an acid radical having a pKa of 7 or less or an alkali metal or ammonium salt thereof; R _{1 represents} a hydrogen atom, an alkyl group or a halogen atom; a, b, d and e are each 0 or 1; and t represents an integer of 1 to 3.

In formulas (I) and (II), A is preferably -COO- or -CONH-; B is preferably a phenylene group or a phenylene group substituted with a hydroxy group, a halogen atom or an alkyl group; D and E are each preferably an alkylene group or a divalent linking group represented by formula C _n H _2n O, C _n H _2n S or C _n H _{2n + 1} N; G is preferably a trivalent linking group represented by formula C _n H _2n-1 , C _n H _2n-1 O, C _n H _2n-1 S or C _n H _2n N (wherein n represents an integer of 1 to 12) ; Each of X and X 'is preferably a carboxy group, a sulfo group, a phospho group, a sulfuric monoester group or a phosphoric monoester group; R ₁ is preferably a hydrogen atom or an alkyl group; and it is preferable that a and b each being 0 or 1 are not 0 at the same time.

Of the monomers A having an acid radical, there are those of the formula (I) wherein B is a phenylene group or a phenylene group substituted with a hydroxy group or an alkyl group having 1 to 3 carbon atoms; D represents an alkylene group having 1 or 2 carbon atoms or an alkyleneoxy group having 1 or 2 carbon atoms; R _{1 is} a hydrogen atom or a methyl group; X is a carboxy group; a is 0; and b is 1.

Specific but non-limiting examples of monomer A with an acid radical are shown below together with their Rf values.
Acrylic acid (Rf: 0.09)
Methacrylic acid (Rf: 0.09)
Maleic acid (Rf: 0.00)

Useful monomer (A) further includes on:

Monomer B is a monomer with one Onium group.

worin J eine divalente Verknüpfungsgruppe darstellt; K eine aromatische Gruppe oder eine substituierte aromatische Gruppe darstellt; M jeweils eine divalente Verknüpfungsgruppe darstellt; Y₁ ein Atom der Gruppe V des Periodensystems darstellt; Y₂ ein Atom der Gruppe VI des Periodensystems darstellt; Z^–1 ein Gegenanion darstellt; R₂ ein Wasserstoffatom, eine Alkylgruppe oder ein Halogenatom darstellt; R₃, R₄, R₅ und R₇ jeweils ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkylgruppe, eine substituierte oder unsubstituierte aromatische Gruppe oder eine substituierte oder unsubstituierte Aralkylgruppe darstellen; R₆ eine Alkylidengruppe oder eine substituierte Alkylidengruppe darstellt; R₃ und R₄ oder R₆ und R₇ zur Bildung eines Rings zusammengenommen werden können; j, k und m jeweils 0 oder 1 darstellen; und u eine ganze Zahl von 1 bis 3 darstellt.Monomer (B) having an onium group is represented by formula (III), (IV) or (V):

wherein J represents a divalent linking group; K represents an aromatic group or a substituted aromatic group; Each M is a divalent linking group; Y _{1 represents} an atom of Group V of the Periodic Table; Y _{2 represents} an atom of Group VI of the Periodic Table; Z ^{-1 represents} a counter anion; R _{2 represents} a hydrogen atom, an alkyl group or a halogen atom; R ₃ , R ₄ , R ₅ and R ₇ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted aralkyl group; R _{6 represents} an alkylidene group or a substituted alkylidene group; R ₃ and R ₄ or R ₆ and R ₇ may be taken together to form a ring; j, k and m are each 0 or 1; and u represents an integer of 1 to 3.

Of the monomers B having an onium group, preferred are those of the formulas (III) to (V) wherein J is -COO- or -CONH-; K is a phenylene group or a phenylene group substituted with a hydroxy group, a halogen atom or an alkyl group; M is an alkylene group or a divalent linking group represented by C _n H _2n O, C _n H _2n S or C _n H _{2n + 1} N (wherein n is an integer of 1 to 12); Y _{1 is} a nitrogen atom or a phosphorus atom; Y _{2 is} a sulfur atom; Z ^{- is} a halide ion, PF ₆ ^- , BF ₄ ^- or R ₈ SO ₃ ^- ; R _{2 is} a hydrogen atom or an alkyl group; R ₃ , R ₄ , R ₅ and R _{7 are} each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group or a substituted or unsubstituted aralkyl group; R _{6 is} a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms; R ₄ and R ₅ , or R ₆ and R ₇ can be taken together to form a ring; and j, k and m are each 0 or 1; provided that j and k do not represent 0 at the same time.

Particularly preferred are those of the formula (III) to (V) wherein K is a phenylene group or a phenylene group substituted with an alkyl group having 1 to 3 carbon atoms; M is an alkylene group having 1 or 2 carbon atoms or an alkyleneoxy group having 1 or 2 carbon atoms; Z ^{-1 is} a chloride ion or R ₈ SO ₃ ^- ; R _{2 is} a hydrogen atom or a methyl group; j is 0; and k is 1.

Specific but not limiting Examples of monomer B having an onium group are together below shown with their Rf value.

Monomer B further includes compounds a 4-crown ether group or a 6-crown ether group.

It is desirable that the polymer, which can be used in the intermediate layer comprises: 5 mol% or more, preferably 10 mol% or more and more preferably 15 to 95 mol% of unit A and 1 mol% or more, preferably 5 mol% or more and more preferably 5 to 85 mol% of unit B. When the content On unit A is 5 mol% or more, the removability in Developing with an alkali continues to accelerate. If the salary on unit B is 1 mol% or more, the adhesion improvement becomes further improved due to synergistic effects together with Unit A.

The polymer may comprise two or more types of unit A or two or more types of unit B. The intermediate layer may contain two or more polymers of different types on unit A or B, Copolymerization ratio of units A and B or molecular weight are included.

Typical examples of the polymer are shown below. The copolymerization ratios are by molar proportions specified.

The polymer is usually by radical successive polymerization (see F.W. Billmeyer, Textbook of Polymer Science, 3rd Edition, Wiley-Interscience (1984)).

While the polymer has a broad molecular weight range can, is it for the polymer prefers a weight average molecular weight (Mw) from 500 to 2,000,000, especially 2,000 to 600,000 by light scattering methods. While the content of unreacted Monomer can vary widely, it is preferably not more than 20 wt .-%, in particular not more than 10 wt .-%.

A Synthesis Example of the Polymer is described below.

SYNTHESIS EXAMPLE

Synthesis of p-vinylbenzoic acid-vinylbenzyltrimethylammonium chloride copolymer (Number 1):

In a 1-liter three-necked flask were 146.9 g (0.99 mol) of p-vinylbenzoic acid (available from Hokko Chemical Industry Co., Ltd.), 44.2 g (0.21 mol) of vinylbenzyltrimethylammonium chloride and 446 g of 2-methoxyethanol and the resulting mixture with stirring in a stream of nitrogen at 75 ° C heated. Then, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was maintained at 75 ° C Blend and stir continued. After 2 hours stirring 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) were added and stirring continued. After 2 hours, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added and stirring for further 2 hours continued. After cooling allowed to come to room temperature, the reaction mixture with stirring in Poured 12 l of ethyl acetate. The precipitated solid was passed through Collected and dried to give 189.5 g of a solid product. The product had a weight average molecular weight (Mw) of 32,000 measured by a light scattering method.

Other to be used according to the invention Polymers can be synthesized similarly become.

The intermediate layer containing the Polymer, is formed on an aluminum plate, which, as below described, made water wettable by various methods has been. For example, the polymer becomes in an organic solvent (eg, methanol, ethanol, methyl ethyl ketone) or a mixture such organic solvents and water dissolved and the solution is applied to an aluminum plate and dried. alternative is an aluminum plate in the polymer solution for adsorption of the polymer dipped, followed by washing with z. As water and dried to form an organic intermediate layer. In the former procedure the concentration of the polymer in the coating solution is 0.005 to 10% by weight. The solution is produced by various coating methods, such as bar coating, Spin coating, spray coating, Steinberg coating, etc., applied. In the latter method is the concentration of the polymer in the dipping solution 0.01 to 20 wt .-% and preferably 0.05 to 5 wt .-% and the dipping is at a liquid temperature from 20 to 90 ° C and preferably 25 to 50 ° C for 0.1 Seconds to 20 minutes, preferably 2 seconds to 1 minute carried out.

The polymer solution can be brought to a pH of 0 to 12 and preferably 0 to 5 are set with basic Substances such as ammonia, triethylamine and potassium hydroxide; organic acidic substances, such as inorganic acids, e.g. For example, hydrochloric acid, phosphoric acid, sulfuric acid and Nitric acid, organic sulfonic acids, z. B. nitrobenzene sulfonic acid and naphthalenesulfonic acid, organic phosphonic acids, z. B. phenylphosphonic and organic carboxylic acids, z. B. benzoic acid, coumaric acid and malic acid; and organic acid chlorides, such as naphthalenesulfonyl chloride and benzenesulfonyl chloride. The polymer solution can a yellow dye for improving hue reproducibility of the photosensitive lithographic printing plate.

The dry coating weight of the polymer is suitably 2 to 100 mg / m ² and preferably 5 to 50 mg / m ² . At a dry coating weight of more than 2 mg / m ² or more than 100 mg / m ² , sufficient effects can not be obtained.

The positive-working photosensitive The lithographic printing plate of the present invention will be detailed in the order of (1) aluminum plate, (2) photosensitive composition and (3) developer solution, described. In the present invention, the photosensitive lithographic printing plate often referred to as "PS plate".

(1) CARRIER

The positive in the invention the lithographic printing plate used and the Treatment thereof are described below.

[ALUMINUM PLATE]

The aluminum plate which can be used as the substrate in the present invention is a plate made of pure aluminum or an aluminum alloy containing a trace of e.g. B. 10 wt .-% or less of heteroatoms, such as silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. Pure aluminum is preferred. Since 100% pure aluminum is difficult to produce by the prior art refining methods, aluminum having a minimum heteroatom content is advantageously used. In practice, aluminum alloys of about 10% by weight or less, as described above, may be considered useful in the present invention. In other words, the aluminum plate used in the present invention is not particularly limited in its composition, and well-known and commonly used materials can be used. Preferred materials include JIS A 1050, 1100, 1200, 3003, 3103, and 3005. The verwen in the present invention dete aluminum plate is about 0.1 to 0.6 mm thick. If necessary, the aluminum plate with z. Example, a surfactant or an aqueous alkali solution for removing a rolling oil on the surface before surface graining cleaned.

[SURFACE TREATMENT GRAIN AND ANODIZATION TREATMENT]

The surface of the aluminum plate becomes mechanically, electrochemically or chemically grained. Mechanical surface graining includes ball graining, brush graining, compressed air graining and Polishing grit on. Electrochemical graining (electrochemical solution the substrate surface) is in an electrolytic solution, containing hydrochloric acid or nitric acid, performed with a AC or DC. Mechanical graining and electrochemical graining can used in combination as disclosed in JP-A-54-63902 (The term "JP-A" as used herein means an "unexamined published Japanese Patent Application ").

If desired, the grained aluminum plate is etched with an alkali and neutralization. The plate will then anodized to increased Water wettability and abrasion resistance to achieve. The one in the Anodizing electrolyte to use can be anything, that one porous Oxide layer can form, usually Sulfuric acid, Phosphoric acid, oxalic acid, chromic acid or a mixture of them. The electrolyte concentration depends on of the kind.

In order to be variable according to the kind of the electrolyte, the anodization conditions are not generally specified. The anodization is usually carried out at an electrolyte concentration of 1 to 80 wt .-%, a liquid temperature of 5 to 70 ° C, a current density of 5 to 60 A / dm ² , a voltage of 1 to 100 V and an electrolysis time of 10 seconds 5 minutes.

The anodized layer is preferably formed to an amount of 1.0 g / m ² or more, more preferably 2.0 to 6.0 g / m ² . If the amount of the anodized layer is less than 1.0 g / m ² , the resultant lithographic printing plate is liable to have an insufficient printing life or is susceptible to scratches on its non-image area to which ink adheres.

While the anodization treatment is applied to the printing side of a lithographic plate, an anodized layer having a weight of 0.01 to 3 g / m ^{2 is also} usually formed on the back side because electric field lines go to the back side.

[WASSERBENETZBARKEITSBEHANDLUNG]

The anodized aluminum plate is then rendered water-wettable by conventional treatments, such as treatment with an alkali metal silicate (eg, an aqueous solution of sodium silicate) as disclosed in U.S. Pat US 2,714,066 , 3,181,461, 3,280,734 and 3,902,734, wherein a substrate is immersed or electrolyzed in an aqueous solution of sodium silicate; a treatment with potassium fluorozirconate as disclosed in JP-B-36-22063 (the term "JP-B" as used herein means an "examined published Japanese patent application"); and a treatment with polyvinylphosphonic acid, as suggested in US Pat US 3,276,868 . 4,153,461 and 4 689 272 , The treatment with a silicate is particularly preferred in the present invention.

[SILICATE TREATMENT]

The silicate treatment is by Immersing the anodized layer of the aluminum plate in an aqueous alkali metal silicate solution with a concentration of 0.001 to 30 wt .-%, preferably 0.005 to 10% by weight and a pH of 10 to 13 (at 25 ° C) at a prescribed liquid temperature for a prescribed Time, z. B. at 15 to 80 ° C. for 0.4 up to 120 seconds. If the pH of the solution is lower than 10, the solution gels. If the pH is higher is 13.0, the anodized layer is dissolved. Suitable alkali metal silicates conclude Sodium silicate, potassium silicate and lithium silicate. To the pH the solution to increase, can Hydroxides, such as sodium hydroxide, potassium hydroxide and lithium hydroxide, be added. The treatment solution may be an alkaline earth metal salt or a salt of the Group IVB metal. The alkaline earth metal salt shoots Nitrates, such as calcium nitrate, strontium nitrate, magnesium nitrate and barium; and water-soluble Salts such as sulfate, hydrochloride, phosphate, acetate, oxalate and borate on. The salt of the Group IVB metal includes Titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, Titanium sulfate, titanium tetraiodide, zirconium oxychloride, zirconium dioxide and Zirconium tetrachloride. The alkaline earth metal salts and the group IVB metal salts can either individually or as a combination of two or more thereof. The metal salt is used in an amount of preferably 0.01 to 10 Wt .-% and more preferably added 0.05 to 5.0 wt .-% based on the treatment solution. The silicate-treated aluminum plate has particularly improved Water wettability for providing non-image areas to which ink hardly adheres, d. H. Non-image areas with improved stain resistance.

[BACK COATING]

If desired, a back coating is provided on the back side of the substrate. The back coat preferably comprises an organic polymer compound described in JP-A-5-45885 or a metal oxide described in JP-A-6-35174, which is obtained by hydrolyzing an organic or inorganic metal compound followed by polycondensation. Among these back coat substances, metal oxides are produced from silicon alkoxides such as Si (OCH _{3) 4,} Si (OC ₂ H _{5) 4,} Si (OC ₃ H _{7) 4} and Si (OC ₄ H _{9) 4,} particularly preferably because of their high resistance against development processing and cheapness and availability of the starting silicon alkoxides.

(2) LIGHT SENSITIVE COMPOSITION

The positive in the invention working photosensitive lithographic printing plate used Photosensitive composition is described in detail below.

The positive-working photosensitive Layer of the lithographic plate is made of a photosensitive Composition produced. Any photosensitive composition, their solubility or swellability in or with a developing solution Changed exposure with light, is useful. Typical examples of photosensitive compositions are described below for illustrative Purposes, but not for limitation described.

Photosensitive compounds used in the photosensitive composition include o-quinone diazide compounds such as o-naphthoquinone diazide compounds. The o-naphthoquinonediazide compounds preferably include an ester of 1,2-diazonaphthoquinone sulfonyl chloride and a pyrogallol acetone resin described in JP-B-43-28403 and an ester of 1,2-diazonaphthoquinone sulfonyl chloride and a phenol-formaldehyde resin described in EP-B-43-28403 US 3,046,120 and 3,188,210 on.

Others from a large number o-naphthoquinonediazide compounds known in patents are also useful. It can z. Example: JP-A-47-5303, JP-A-48-63802, JP-A-48-63803 JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, JP-B-37-18015, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481, JP-A-5-11444, JP-A-5-19477, JP-A-5-19478, JP-A-5-107755, U.S. Patents 2,797,213, 3,454,400, 3,544,323, 3,573 917, 3,674,495 and 3,785,825, British Patents 1,227,602, 1,251,345, 1,267 005, 1 329 888 and 1 330 932 and DE-PS 854 890.

o-naphthoquinonediazide available by reacting a polyhydroxy compound having a molecular weight of 1,000 or less and a 1,2-diachonathoquinone sulfonyl chloride also useful. It can JP-A-51-139402, JP-A-58-150948, JP-A-58-203434, JP-A-59-165053, JP-A-60-121445, JP-A-60-134235, JP-A-60-163043, JP-A-61-118744, JP-A-62-10645, JP-A-62-10646, JP-A-62-153950, JP-A-62-178562, JP-A-64-76047, U.S. Patents 3,102,809, 3,126,281, 3,130,047, 3,148,983, 3,184,310, 3,188,210 and 4,639,406.

In the synthesis of these o-naphthoquinone diazide compounds the 1,2-diazonaphthoquinonesulfonyl chloride is added in an amount of 0.2 to 1.2 equivalents, in particular 0.3 to 1.0 equivalents reacted with the hydroxy group of the polyhydroxy compound. The 1,2-diazonaphthoquinone sulfonyl chloride is preferably a 1,2-diazonaphthoquinone-5-sulfonyl chloride. 1,2-diazonaphthoquinone-4-sulfonyl chloride is also useful. The Reaction gives a mixture of o-naphthoquinone diazide compounds, the different in the position and / or the amount of introduced 1,2-Diazonaphthochinonsulfonsäureestergruppe are. It is preferred that the mixture be a fully esterified compound contains d. H. a compound in which all hydroxy groups with the sulfonic acid group esterified in a proportion of 5 mol% or more, especially 20 to 99 mol% are.

Positive-working photosensitive Compounds that replace the o-naphthoquinonediazide compounds can be used conclude a: polymer compounds having an o-nitrile carbinol ester group, described in JP-B-52-2696, pridinium-containing compounds (JP-A-4-365049) and diazonium-containing compounds (JP-A-5-249664, JP-A-6-83047, JP-A-6-324495 and JP-A-7-72621).

Compounds containing an acid Releasing photolysis (JP-A-4-121748 and JP-A-4-365043) combined with Compounds with a C-O-C group or a C-O-Si group which on contact with an acid can be released also be used. For example, a compound that adds an acid photolysis, combined with an acetal or an O, N-acetal compound (JP-A-48-89003), an orthoester or an aminoacetal compound (JP-A-51-120714), a polymer having an acetal or ketal group in the main chain thereof (JP-A-53-133429), an enol ether compound (JP-A-55-12995, JP-A-4-19748 and JP-A-6-230574), an N-acylimino-plastic compound (JP-A-55-126236), a polymer having an orthoester group in the Main chain thereof (JP-A-56-17345), a polymer having a silyl ester group (JP-A-60-10247) or a silyl ether compound (JP-A-60-37549, JP-A-60-121446, JP-A-63-236028, JP-A-63-236029 and JP-A-63-276046).

Above-mentioned positive-working photosensitive compounds or combinations become übli used in an amount of 10 to 50 wt .-%, and preferably 15 to 40 wt .-% based on the photosensitive composition.

The o-quinone diazide compound can itself constitute a photosensitive layer, but is preferred together with one in an aqueous one alkaline solution soluble Binder resin used. Such soluble in an aqueous alkali solution Close Resins a: Novolak resins, such as phenol-formaldehyde resins, m- and / or p-cresol-formaldehyde resins and phenol / m-, p-, o- or m- / p- / o-mixed cresol-formaldehyde resins. These alkali-soluble Resins preferably have a weight average molecular weight of 500 to 100,000.

Resole type phenolic resins are also suitable as a binder. Phenol / m, p, o or m / p / o mixed cresol-formaldehyde resins are preferred. The phenolic resins described in JP-A-61-217034 are particularly preferred.

• (1) Acrylamide, Methacrylamide, Acrylsäureester, Methacrylsäureester und Hydroxystyrol, enthaltend eine aromatische Hydroxygruppe, wie N-(4-Hydroxyphenyl)acrylamid oder N-(4-Hydroxyphenyl)methacrylamid, o-, m- oder p-Hydroxystyrol, o- oder m-Brom-p-hydroxystyrol, o- oder m-Chlor-p-hydroxystyrol und o-, m- oder p-Hydroxyphenylacrylat oder Methacrylat.
• (2) Ungesättigte Carbonsäuren, wie Acrylsäure, Methacrylsäure, Maleinsäure oder ein Anhydrid oder ein Halbester davon und Itaconsäure oder ein Anhydrid oder Halbester davon.
• (3) Ungesättigte Sulfonamide, einschließlich Acrylamiden, wie N-(o-Aminosulfonylphenyl)acrylamid, N-(m-Aminosulfonylphenyl)acrylamid, N-(p-Aminosulfonylphenyl)acrylamid, N-[1-(3-Aminosulfonyl)naphthyl]acrylamid und N-(2-Aminosulfonylethyl)acrylamid; Methylacrylamide, wie N-(o-Aminosulfonylphenyl)methacrylamid, N-(m-Aminosulfonylphenyl)methacrylamid, N-(p-Aminosulfonylphenyl)methacrylamid, N-[1-(3-Aminosulfonyl)naphthyl]methacrylamid und N-(2-Aminosulfonylethyl)methacrylamid; Acrylsäureester, wie o-Aminosulfonylphenylacrylat, m-Aminosulfonylphenylacrylat, p-Aminosulfonylphenylacrylat und 1-(3-Aminosulfonylphenylnaphthyl)acrylat; und Methacrylsäureester, wie o-Aminosulfonylphenylmethacrylat, m-Aminosulfonylphenylmethacrylat, p-Aminosulfonylphenylmethacrylat und 1-(3-Aminosulfonylphenylnephthyl)methacrylat.
• (4) Substituierte oder nicht-substituierte Phenylsulfonylacrylamide, wie Tosylacrylamid und substituierte oder nicht-substituierte Phenylsulfonylmethacrylamid, wie Tosylmethacrylamid. Die filmbildenden Vinylharze können ferner eine Comonomereinheit enthalten, erhalten aus zusätzlich zu den oben aufgeführten Monomeren nachstehend gezeigten Monomergruppen (5) bis (14).
• (5) (Meth)acrylsäureester mit einer aliphatischen Hydroxygruppe, wie 2-Hydroxyethyl(meth)acrylat.
• (6) Substituierte oder nicht-substituierte Acrylsäureester, wie Methylacrylat, Ethylacrylat, Propylacrylat, Butylacrylat, Amylacrylat, Hexylacrylat, Cyclohexylacrylat, Octylacrylat, Phenylacrylat, Benzylacrylat, 2-Chlorethylacrylat, 4-Hydroxybutylacrylat, Glycidylacrylat und N-Dimethylaminoethylacrylat.
• (7) Substituierte oder nicht-substituierte Methacrylsäureester, wie Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, Butylmethacrylat, Amylmethacrylat, Hexylmethacrylat, Cyclohexylmethacrylat, Octylmethacrylat, Phenylmethacrylat, Benzylmethacrylat, 2-Chlorethylmethacrylat, 4-Hydroxybutylmethacrylat, Glycidylmethacrylat und N-Dimethylaminoethylmethacrylat.
• (8) (Meth)acrylamaide, wie (Meth)acrylamid, N-Methylol(meth)acrylamid, N-Ethyl(meth)acrylamid, N-Hexyl(meth)acrylamid, N-Cyclohexyl(meth)acrylamid, N-Hydroxyethyl(meth)acrylamid, N- Phenyl(meth)acrylamid, N-Benzyl(meth)acrylamid, N-Nitrophenyl(meth)acrylamid und N-Ethyl-N-phenyl(meth)acrylamid.
• (9) Vinylether, wie Ethylvinylether, 2-Chlorethylvinylether, Hydroxyethylvinylether, Propylvinylether, Butylvinylether, Octylvinylether und Phenylvinylether.
• (10) Vinylester, wie Vinylacetat, Vinylchloracetat, Vinylbutyrat und Vinylbenzoat.
• (11) Styrol oder Derivate hiervon, wie α-Methylstyrol, Methylstyrol und Chlormethylstyrol.
• (12) Vinylketone, wie Methylvinylketon, Ethylvinylketon, Propylvinylketon und Phenylvinylketon.
• (13) Olefine, wie Ethylen, Propylen, Isobutylen, Butadien und Isopren.
• (14) N-Vinylpyrrolidon, N-Vinylcarbazol, 4-Vinylpyridin, Acrylonitril, Methacrylonitril, usw.

The photosensitive composition may also contain other various alkali-soluble resins such as phenol-modified xylene resin, polyhydroxystyrene, poly (halogenated hydroxystyrene), acrylic resins having a phenolic hydroxy group as disclosed in JP-A-51-34711, vinyl resins or urethane resins having a sulfonamide group disclosed in JP -A-2-866 and vinyl resins having the structural unit described in JP-A-7-28244, JP-A-7-36184, JP-A-7-36185, JP-A-7-248628, JP-A- 7-261394 and JP-A-7-333839. In particular, it is preferable that the vinyl resins are film-forming resins comprising at least one kind of units obtainable from alkali-soluble group-containing monomer groups (1) to (4) shown below.

• (1) acrylamides, methacrylamides, acrylic esters, methacrylic acid esters and hydroxystyrene containing an aromatic hydroxy group such as N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene and o-, m- or p-hydroxyphenyl acrylate or methacrylate.
• (2) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid or an anhydride or a half ester thereof and itaconic acid or an anhydride or half ester thereof.
• (3) Unsaturated sulfonamides including acrylamides such as N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide and N- (2-aminosulfonylethyl) acrylamide; Methylacrylamides such as N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide and N- (2-aminosulfonylethyl ) methacrylamide; Acrylic acid esters such as o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate; and methacrylic acid esters such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate and 1- (3-aminosulfonylphenyl-nephthyl) methacrylate.
• (4) Substituted or unsubstituted phenylsulfonylacrylamides such as tosylacrylamide and substituted or unsubstituted phenylsulfonylmethacrylamide such as tosylmethacrylamide. The film-forming vinyl resins may further contain a comonomer unit obtained from monomer groups (5) to (14) shown in addition to the above-mentioned monomers shown below.
• (5) (Meth) acrylic acid ester having an aliphatic hydroxy group such as 2-hydroxyethyl (meth) acrylate.
• (6) Substituted or non-substituted acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate.
• (7) Substituted or non-substituted methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate and N-dimethylaminoethyl methacrylate.
• (8) (Meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, N-ethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-hydroxyethyl ( meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-nitrophenyl (meth) acrylamide and N-ethyl-N-phenyl (meth) acrylamide.
• (9) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.
• (10) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
• (11) styrene or derivatives thereof, such as α-methylstyrene, methylstyrene and chloromethylstyrene.
• (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.
• (13) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
• (14) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc.

These alkali-soluble polymers are preferably a weight average molecular weight from 500 to 500,000.

These alkali-soluble polymers may be used either singly or in combination of two or more thereof. From the viewpoint of development characteristics and press life, the alkali-soluble polymers in a proportion of not more than 99% by weight, preferably 30 to 95% by weight, and more preferably 50 to 95% by weight based on the photosensitive composition.

It is preferable for obtaining improved ink receptivity that the photosensitive composition is a condensate of a phenol substituted with an alkyl group having 3 to 8 carbon atoms and formaldehyde such as t-butylphenol-formaldehyde resin or an octylphenol-formaldehyde resin as described in U.S. Pat US 4,123,279 , or an o-naphthoquinonediazide sulfonic acid ester of the condensate such as that described in JP-A-61-243446.

[DEVELOPMENT ACCELERATOR]

For improving the sensitivity and developing characteristics, it is preferable to add a cyclic acid anhydride, a phenol compound and an organic acid to the photosensitive composition as a development accelerator. Suitable cyclic acid anhydrides are described in US 4,115,128 including phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride and pyromellitic anhydride. Suitable phenolic compounds including bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane and 4,4' , 3 '', 4 '' - tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane. Suitable organic acids are described in JP-A-60-88942 and JP-A-2-96755, including sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphonic acid esters and carboxylic acids. Specific examples of the acids are p-toluenesulfonic acid, dodecylbenzenesulfonic acids, p-toluenesulfonic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenylphosphate, diphenylphosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene -2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and amino acids. The content of the development accelerator in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

[DEVELOPMENT STABILIZER]

The photosensitive composition may be nonionic surfactants (JP-A-62-251740 and JP-A-4-68355) or amphoteric surfactants (JP-A-59-121044 and JP-A-4-13149) the development latitude, d. H. Development stability under Development conditions, to improve.

Suitable nonionic surfactants conclude a: sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, Glycerol monostearate, polyoxyethylene sorbitan monoleate and polyoxyethylene nonylphenyl ether.

Suitable amphoteric surfactants include: Alkyldi (aminoethyl) glycines, alkylpolyaminoethylglycine hydrochlorides, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium, N-tetradecyl-N, N-betaine (e.g., Amogen K, manufactured by Daiichi Kogyo K.K.) and alkylimidazoline compounds (e.g., Levon 15, manufactured by Sanyo Chemical Industries, Ltd.).

The content of these surfactants in the Photosensitive composition is preferably 0.05 to 15 wt .-% and more preferably 0.1 to 5% by weight.

[COPIER, DYE AND OTHER]

The photosensitive composition can be a copy-out agent (print-out agent) to make a visible image when exposed, a dye as image dye and a filler contain. Useful dyes conclude the basic dyes described in JP-A-5-313359, which from a cation with a basic dye skeleton and from one organic anion having 10 or more carbon atoms, a sulfo group as the only exchangeable group, and 1 to 3 hydroxy groups. The dyes are based in an amount of 0.2 to 5 wt .-% based the total composition used.

To the photosensitive composition may be added one or more compounds which produce a photolysis product which can interact with the dyes described in JP-A-5-313359 supra to change hue, such as o-naphthoquinone diazide-4 sulfonyl halide described in US 3,969,118 (JP-A-50-36209), a trihalomethyl-2-pyrone or trihalomethyltriazine described in US 4,160,671 (JP-A-53-36223), various o-naphthoquinonediazide compounds described in US 2,038,801 (JP-A-55-62444) and a 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound described in US 4,279,982 (JP-A-55-77742). Of these compounds, those having an absorption of 400 nm can also serve as the above-described yellow dye.

Other dyes can also be used as image-coloring agents. Suitable dyes, including salt-forming organic dyes, include: oil-soluble dyes and basic dyes, such as Oil Green BG, Oil Blue BOS and Oil Blue # 603 (all manufactured by Orient Kagaku Kogyo KK); Victoria Pure Blue BOH, Victoria Pure Blue NAPS and Ethyl Violet 6HNAPS (all manufactured by Hodogaya Chemical Co., Ltd.); Rhodamine B (CI 45170B), malachite green (CI 42000) and methylene blue (CI 52015).

worin R₁ und R₂ jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, Arylgruppe oder Alkenylgruppe darstellen oder R₁ oder R₂ zusammengenommen werden können zur Bildung eines Rings; R₃, R₄ und R₅ jeweils ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellen; G₁ und G₂ jeweils eine Alkoxycarbonylgruppe, Aryloxycarbonylgruppe, Acylgruppe, Arylcarbonylgruppe, Alkothiogruppe, Arylthiogruppe, Alkylsulfonylgruppe, Arylsulfonylgruppe oder Fluoralkylsulfonylgruppe darstellen oder G₁ und G₂ können zur Bildung eines Rings zusammengenommen werden; mindestens eine der R₁, R₂, R₃, R₄, R₅, G₁ und G₂ weist mindestens eine Sulfongruppe, Carboxygruppe, Sulfonamidgruppe, Imidgruppe, N- Sulfonylamidgruppe, Phenolhydroxygruppe, Sulfonimidgruppe, Metallsalz dieser Gruppen und ein organisches oder anorganisches Ammoniumsalz dieser Gruppen auf; Y stellt ein divalentes Atom oder eine Atomgruppe, ausgewählt aus O, S, NR (worin R eine Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe darstellt), Se, -C(CH₃)₂ und -CH=CH- dar; und n₁ stellt 0 oder 1 dar.

worin R₆ und R₇ jeweils ein Wasserstoffatom, eine Alkylgruppe, substituierte Alkylgruppe, Arylgruppe, substituierte Arylgruppe, heterocyclische Gruppe, substituierte heterocyclische Gruppe, Allylgruppe oder substituierte Allylgruppe darstellen oder R₆ und R₇ können miteinander verbunden sein zur Bildung eines Rings zusammen mit den entsprechenden Kohlenstoffatomen, an das sie gebunden sind; n₂ stellt 0, 1 oder 2 dar; G₃ und G₄ stellen jeweils ein Wasserstoffatom, eine Cyanogruppe, Alkoxycarbonylgruppe, substituiertes Alkoxycarbonylgruppe, Aryloxycarbonylgruppe, substituierte Aryloxycarbonylgruppe, Acylgruppe, substituierte Acylgruppe, Arylcarbonylgruppe, substituierte Arylcarbonylgruppe, Alkylthiogruppe, Arylthiogruppe, Alkylsulfonylgruppe, Arylsulfonylgruppe oder Fluoralkylsulfonylgruppe dar, vorausgesetzt dass G₃ und G₄ nicht gleichzeitig ein Wasserstoffatom darstellen; G₃ und G₄ können miteinander verbunden sein zur Bildung eines Rings aus nicht-metallischen Atomen zusammen mit dem Kohlenstoffatom, an das sie gebunden sind; und mindestens eine der R₆, R₇, G₃ und G₄ weist mindestens eine aus einer Sulfogruppe, Carboxygruppe, Sulfonamidgruppe, Imidgruppe, N-Sulfonylamidgruppe, phenolisches Hydroxygruppe, Sulfonimidgruppe, Metallsalz dieser Gruppen und einem organischen oder anorganischen Ammoniumsalz dieser Gruppen auf.

worin R₈, R₉, R₁₀, R₁₁, R₁₂ und R₁₃, die gleich oder unterschiedlich sein können, jeweils darstellen: ein Wasserstoffatom, eine Alkylgruppe, substituierte Alkylgruppe, Arylgruppe, substituierte Arylgruppe, substituierte Arylgruppe, Alkoxygruppe, Hydroxygruppe, Acylgruppe, Cyanogruppe, Alkoxycarbonylgruppe, Aryloxycarbonylgruppe, Nitrogruppe, Carboxygruppe, Chloratom oder Bromatom.The photosensitive composition may be yellow dyes represented by the following formulas (VI), (VII) or (VIII) whose absorbance at 417 nm is 70% or more at 436 nm.

wherein R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, aryl group or alkenyl group, or R ₁ or R ₂ may be taken together to form a ring; R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; G ₁ and G ₂ each represents an alkoxycarbonyl group, aryloxycarbonyl group, acyl group, arylcarbonyl group, alkothio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or fluoroalkylsulfonyl group, or G ₁ and G ₂ may be taken together to form a ring; at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , G ₁ and G ₂ has at least one sulfone group, carboxy group, sulfonamide group, imide group, N-sulfonylamide group, phenol hydroxy group, sulfonimide group, metal salt of these groups and an organic or inorganic Ammonium salt of these groups; Y represents a divalent atom or an atomic group selected from O, S, NR (wherein R represents a hydrogen atom, an alkyl group or an aryl group), Se, -C (CH ₃ ) ₂ and -CH = CH-; and n ₁ represents 0 or 1.

wherein R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, substituted alkyl group, aryl group, substituted aryl group, heterocyclic group, substituted heterocyclic group, allyl group or substituted allyl group, or R ₆ and R ₇ may be bonded to each other to form a ring together with corresponding carbon atoms to which they are attached; n ₂ represents 0, 1 or 2; G ₃ and G ₄ each represent a hydrogen atom, a cyano group, alkoxycarbonyl group, substituted alkoxycarbonyl group, aryloxycarbonyl group, substituted aryloxycarbonyl group, acyl group, substituted acyl group, arylcarbonyl group, substituted arylcarbonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or fluoroalkylsulfonyl group, provided that G ₃ and G _{4 are} not simultaneously a hydrogen atom; G ₃ and G ₄ may be linked together to form a ring of non-metallic atoms together with the carbon atom to which they are attached; and at least one of R ₆ , R ₇ , G ₃ and G ₄ has at least one of a sulfo group, carboxy group, sulfonamide group, imide group, N-sulfonylamide group, phenolic hydroxy group, sulfonimide group, metal salt of these groups and an organic or inorganic ammonium salt of these groups.

wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , which may be the same or different, each represent a hydrogen atom, an alkyl group, substituted alkyl group, aryl group, substituted aryl group, substituted aryl group, alkoxy group, hydroxy group, Acyl group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, carboxy group, chlorine atom or bromine atom.

The photosensitive lithographic printing plate of the present invention is obtained by applying a photosensitive solution of the photosensitive composition in a solvent capable of dissolving each ingredient to the intermediate layer to form a photosensitive layer. Suitable solvents include γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propane, 1-methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethyl acetamide , Dimethyl formamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropyl alcohol and diethylene glycol dimethyl ether. These solvents can be used either singly or as a mixture thereof. The photosensitive solution preferably has a solid content (a concentration of the above-described components) of 2 to 50% by weight. The coating weight is preferably in the range of 0.5 g / m ² to 4.0 g / m ² . If the coating weight is less than 0.5 g / m ² , the lithographic plate has a poor printing life. If it exceeds 4.0 g / m ² , the press life is prolonged but the sensitivity is lowered.

The photosensitive composition may contain surfactants to improve coating properties. For example, you can the fluorine-containing surfactants described in JP-A-62-170950 can be used. The surfactants are preferably used in an amount of from 0.01 to 5% by weight, in particular 0.05 to 1.0 wt .-% based on the total composition added.

Although the thus produced lithographic Printing plate produce accurate impressions of an original film can, there is a lack of focus when exposing and the resulting imprints are rough. It was suggested the surface roughen the photosensitive layer to avoid the lack of sharpness To reduce exposure. For example, JP-A-61-258255 describes the addition from particles of several microns to a photosensitive solution, but this procedure leads only to a small effect in reducing the shortage of sharpness, with no effect in improving the pressure roughness.

The method disclosed in JP-A-50-125805, JP-B-57-6582, JP-B-61-28986 and JP-B-62-62337, which comprises adding such a compound as rough the surface of a photosensitive layer makes noticeable effects of both the lack of sharpness and the pressure roughness. The improvements are further ensured by incorporating a light absorber having an absorption in the photosensitive wavelength region of the photosensitive layer into a matte layer as proposed in JP-B-5-20619. Thus, satisfactory prints can be obtained even if an original film obtained by FM screening and an original film of 300 lines / inch is used, resulting in a lack of sharpness in exposing and printing roughness rather than an original film of 175 lines / inch , The roughened surface of the photosensitive layer preferably has such a surface profile that the height of the projections is in the range of 1 to 40 μm, especially 2 to 20 μm, the size (width) of the projections in the range of 10 to 10,000 μm, in particular 20 to 200 microns and the number of projections from 1 to 1,000, in particular from 5 to 500 per mm ² moves.

(3) DEVELOPMENT TREATMENT

The developmental treatment of photosensitive The lithographic printing plate of the present invention is shown below described.

[EXPOSURE]

The photosensitive lithographic Printing plate (precursor) of the present invention is exposed imagewise and developed. Light sources with active light, for exposure is used, close a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp (pulsed xenon lamp), a tungsten lamp and a chemical lamp on. Rays close an electron beam, X-rays, Ion beam and also infrared rays. g-rays, i-rays, deep UV rays and high-density energy beams (laser beams) are also used. helpful Close the laser Helium-Neon-Laser, Argon-Laser, Krypton-Laser, Helium-Cadminium-Laser, KrF excimer laser, Semiconductor laser and YAG laser.

[DEVELOPER]

A preferred developer for development the photosensitive invention Lithographic printing plate is an alkaline aqueous solution containing essentially no organic solvent. Examples of suitable Developers are watery solutions of sodium silicate, potassium silicate, NaOH, KOH, LiOH, sodium tertiary phosphate, Sodium secondary Phosphate, ammonium tertiary Phosphate, ammonium secondary Phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, Potassium carbonate, aqueous ammonia, etc.

An even more preferred developer is a solution containing (a) at least one non-reducing saccharide and (b) at least one base and having a pH of 9.0 to 13.5.

This developer will be below described in detail. Unless otherwise stated, this means Expression "developer" not just a stock solution, with which initiates development, in the strict sense of the word, but also an adjunct (Replenisher).

[NON-REDUCING SACCHARID AND BASE]

The developer is characterized that the main component thereof is at least one compound selected from comprising non-reducing saccharides and at least one type of base, the pH of the solution in the range of 9.0 to 13.5.

The non-reducing saccharides, which carry no free aldehyde or keto group and no reducing Show property are classified into trehalose-type oligosaccharides, wherein reducing groups linked together, glycosides wherein the reducing group a saccharide with a non-sugar is bound, and sugar alcohols, obtained by reducing Saccharides by hydrogenation, any of which is suitable. The trehalose-type oligosaccharides conclude Sucrose and trehalose. The glycosides include alkyl glycosides, Phenol glycosides and mustard oil glycosides on. Close the sugar alcohols D- or L-arabitol, ribitol, xylitol, D- or L-sorbitol, D- or L-mannitol, D- or L-iditol, D- or L-talitol, dulcitol and allodulcitol on. Maltitol obtained by filtering a disaccharide, and reduced sugar obtained by hydrogenating oligosaccharides, are also suitable. Preferred among these are sugar alcohols and Sucrose. In particular, D-sorbitol, sucrose and are reduced Sugar due to its buffer effect in a suitable pH range and low price preferred.

These non-reducing saccharides be either individually or in combination of two or more of them used. The concentration of non-reducing saccharide (s) in the developer is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. At concentrations less than 0.1%, no enough Buffer effect achieved. Presence of more than 30% of non-reducing saccharides makes It is not only difficult the solution narrow, but leads also to an increase in material costs.

If a reducing saccharide Used in combination with a base, the resulting Developer over time brown and the pH of the developer decreases gradually, which results in a reduction in development performance.

The combined with the non-reducing Saccharide used base includes common alkali. suitable Close the alkali an: inorganic, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, Sodium tertiary Phosphate, potassium tertiary Phosphate, ammonium-tertiary Phosphate, sodium secondary phosphate, Potassium secondary Phosphate, ammonium secondary Phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, Potassium bicarbonate, ammonium bicarbonate, sodium borate, Potassium borate and ammonium borate. Organic alkalis can also can be used, including Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Diisopropanolamine, ethyleneimine, ethylenediamine and pyridine.

These alkalis can be either individually or be used as a combination of two or more. sodium hydroxide and potassium hydroxide are preferred alkali, because the pH of the developer over a wide range by controlling the ratio of this alkali to non-reducing saccharide can be adjusted. Sodium tertiary phosphate, Potassium tertiary Phosphate, sodium carbonate and potassium carbonate are also preferred due to their high buffering effect.

The alkali is added in an amount around the developer to a pH of 9.0 to 13.5 and more preferably 10.0 to 13.2, with the amount of the desired pH and the type and amount of non-reduced used in combination Saccharide depends.

An alkaline buffer solution comprising a weak acid from saccharides and a strong base can be used in combination in the developer be used. Weak acids with a pKa of 10.0 to 13.2 are preferred for use in the buffer solution. Such weak acids can selected are described in the literature, such as Ionization Constants of Organic Acids in Aqueous Solution, Pergamon Press. Examples suitable weak acids are shown below. The values in parentheses are pKa values.

Alcohols, such as 2,2,3,3-tetrafluoropropanol-1 (12.74), trifluoroethanol (12.37) and trichloroethanol (12.24); aldehydes, such as pyridine-1-aldehyde (12.68) and pyridine-4-aldehyde (12.05); Compounds with phenolic Hydroxy group, such as salicylic acid (13.0), 3-hydroxy-2-naphtholic acid (12,84), Catechol (12,6), gallic acid (12.4), sulfosalicylic acid (11,7), 3,4-dihydroxysulfonic acid (12,2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10.33), Resorcinol (11,27), p-cresol (10,27) and m-cresol (10,09); oximes, such as 2-butanone oxime (12.45), acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldoxime (12,10), dimethylglycoxime (11,9), ethanediamine dioxime (11,37) and acetophenone oxime (11,35); Nucleic acid-related substances, such as Adenosine (12.56), inosine (12.5), guanine (12.3), cytosine (12.2), Hypoxanthine (12.1) and xanthine (11.9); and other weak acids, like diethylaminomethylphosphonic (12,32), 1-amino-3,3,3-trifluorobenzoic acid (12,29), isopropylidenediphosphonic (12,10), 1,1-ethylidenediphosphonic acid (11.54), 1-hydroxy-1,1-ethylidenediphosphonic acid (11,52), Benzimidazole (12,86), thiobenzamide (12,8), picolinethioamide (12,55) and barbituric acid (12.5). Preferred of these weak acids are sulfosalicylic acid and Salicylic acid.

The bases suitably with the weak acids can be combined conclude Sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide on. These bases can used either singly or as a combination of two or more thereof become. The concentration and combination of the bases becomes suitable selected, to adjust the pH of the developer in the desired range.

[SURFACTANT]

If desired, the developer various surfactants and organic solvents contain the Accelerate development, disperse foam or ink receptivity the picture surface to increase the pressure plate. Anionic, cationic, nonionic or amphoteric surfactants can be used become.

Examples of suitable nonionic Surfactants are polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, Polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, partial fatty acid esters of Glycerin, partial fatty acid esters of sorbitan, partial fatty acid esters of pentaerythritol, propylene glycol monofatty acid ester, partial fatty acid esters of sucrose, partial fatty acid esters of polyoxyethylene sorbitan, partial fatty acid esters of polyoxyethylene sorbitol, Polyethylene glycol fatty acid ester, partial fatty of polyglycerol, polyoxyethylene castor oil, partial fatty acid esters of polyoxyethylene glycerol, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, Polyoxyethylene alkylamines, triethanolamine fatty acid esters and trialkylamine oxides.

Examples of suitable anionic Surfactants are fatty acid salts, abietic, Hydroxyalkensulfonsäuresalze, alkanesulfonic, Dialkylsulfonsuccinsäureestersalze, (straight-chain) alkylbenzenesulfonic acid salts, (branched) alkylbenzenesulfonic acid salts, alkylnaphthalene, Alkylphenoxypolyoxyethylenepropylsulfonic acid salts, polyoxyethylenealkylsulfonephenyl ether salts, N-methyl-N-oleyltaurinnatriumsalz, N-Alkylsulfonsuccinsäuremonoamiddinatriumsalze, Petroleumsulfonsäuresalze, sulphurised beef fat oil, Sulfurized ester salts of fatty acid alkyl esters, sulfurized Ester salts of glycerol monofatty acid esters, Polyoxyethylene alkylphenyl ether sulfuric ester salts, polyoxyethylene styrylphenyl ether sulfuric acid ester salts, Alkylphosphorsäureestersalze, Polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, partially saponified styrene-maleic anhydride copolymers, partially saponified olefin maleic anhydride copolymers and naphthalenesulfonic acid salt formalin condensates.

Examples of suitable cationic Surfactants are alkylamine salts, quaternary ammonium salts (eg tetrabutylammonium bromide), Polyoxyethylenalkylaminsalz and Polyethylenpolyaminderivate.

Examples of suitable amphoteric surfactants are carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters and imidazoline derivatives.

The surfactants listed above appearing expression "polyoxyethylene" may by others Polyoxyalkylenes, such as polyoxymethylene, polyoxypropylene and polyoxybutylene, be replaced.

Further preferred surfactants are fluorine-containing, which contain a perfluoroalkyl group in the molecule thereof. Such fluorine-containing Close surfactants an: anionic-type compounds such as perfluoroalkylcarboxylic acid salts, perfluoroalkylsulfonic and perfluoroalkyl phosphoric acid ester; Amphoteric type compounds such as perfluoroalkylbetaines; links cationic type such as perfluoroalkyltrimethylammonium salt; and Nonionic type compounds such as perfluoroalkylamine oxides, Perfluoroalkyl ethylene oxide adducts, oligomers containing a perfluoroalkyl group and a hydrophilic group, oligomers containing a perfluoroalkyl group and a lipophilic group, oligomers containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group and urethane containing a perfluoroalkyl group and a lipophilic group.

These surfactants can be used either individually as a combination used by two or more of them. You become a developer in a concentration of 0.001 to 10% by weight, and preferably 0.01 to 5 wt .-% given.

[DEVELOPMENT STABILIZER]

The developer can be different Development stabilizers included. Suitable development stabilizers conclude those described in JP-A-6-282079, such as polyethylene glycol adducts of sugar alcohols, tetraalkylammonium salts, e.g. For example, tetrabutylammonium hydroxide, Phosphonium salts, e.g. B. tetrabutylphosphonium bromide and iodonium salts, z. B. diphenyliodonium chloride.

Other useful development stabilizers include: the anionic or amphoteric surfactants described in JP-A-50-51324, the water-soluble cationic polymers described in JP-A-55-95946, the water-soluble amphoteric polyelectrolytes described in JP-A-56-5. 142528, the alkylene glycol-added organic boron compounds described in JP-A-59-84241, the polyoxyethylene-polyoxypropylene block poly malt type water-soluble surfactants described in JP-A-60-111246, the (polyoxyethylene-polyoxypropylene) -substituted alkylenediamine compounds described in JP-A-60-129750, polyethylene glycol having a weight-average molecular weight of 300 or more, as described in JP-A- 61-215554, fluorine-containing surfactants having a cationic group as described in JP-A-63-275858, water-soluble ethylene oxide adducts obtained by adding 4 moles or more of ethylene oxide to an acid or an alcohol as described in JP-A- 2-39157, and water-soluble polyalkylene compounds.

[ORGANIC SOLVENT]

While the developer used in the present invention substantially no organic solvent as stated above contains can be an organic solvent, if necessary, be added. A suitable organic solvent, which can be added is selected among those with a Water of about 10% by weight or less, preferably 5% by weight or less. Examples such organic solvents are: 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, N-phenylethanolamine and N-phenyldiethanolamine. The term "the developer used above essentially contains no organic solvent "means that the Content of organic solvent, if any, not more than 5% by weight based on the total weight of the developer is. The amount of organic solvent is closely linked with the amount of surfactants. As the organic solvent increases in amount, it is preferable to increase the amount of the surfactant. If an organic solvent in an elevated Quantity without increasing the Amount of surfactant is used dissolves the organic solvent not completely, and leads not sure of satisfactory development characteristics.

[REDUCING AGENT]

The developer can use a reducing agent included to prevent the foam development on the printing plate. Addition of a reducing agent is particularly effective in developing a negative-working photosensitive lithographic printing plate, containing a photosensitive diazonium salt compound in its photosensitive layer. Preferred organic reducing agents conclude a: phenolic compounds, such as thiosalicyclic acid, hydroquinone, methol, methoxyquinone, Resorcinol and 2-methylresorcinol; and amine compounds, such as phenylenediamine and phenylhydrazine. Preferred inorganic reducing agents include: Sodium salt, potassium salt, ammonium salt, etc. of sulfuric acid, hydrogen sulfite, Phosphoric acid, Hydrogen phosphite, primary Phosphite, thiosulphuric acid, dithionic, etc. Of these reducing agents, sulfites are particularly effective to prevent foaming. The reducing agent is preferably in a concentration of 0.05 to 5 wt .-% based on the developer used.

[ORGANIC CARBOXYLIC ACID]

The developer can be an organic Carboxylic acid, preferably an aliphatic or aromatic carboxylic acid with Contain 6 to 20 carbon atoms. Examples of suitable aliphatic carboxylic acids are n-caproic acid, n-heptanoic acid, n-caprylic acid, lauric acid, myristic acid, palmitic acid and Stearic acid, wherein alkanoic acids with 8 to 12 carbon atoms are particularly preferred. The aliphatic Carboxylic acids can be unsaturated with a double bond in the carbon chain or can be a have branched carbon chain.

The aromatic carboxylic acids are Compounds with a benzene ring, a naphthalene ring, an anthracene ring, etc., which is substituted with a carboxy group. Examples of suitable aromatic carboxylic acid are o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid and 2-naphthoic acid, being hydroxynaphthoic acid is particularly effective.

The aliphatic or aromatic carboxylic acid is preferably in the form of its sodium, potassium or ammonium salt used, the improved water solubility over the free form shows. While the organic carboxylic acid content is not particularly limited in the developer, results in a concentration of Less than 0.1 wt .-% to a low effect and a concentration of more than 10% by weight to no further improvement and may be more with the solution of more Additives interact. Accordingly, a preferred concentration range is from 0.1 to 10 wt .-%, in particular 0.5 to 4 wt .-% in the developer.

[OTHER]

The developer may also choose others contain various additives, such as preservatives, dyes, Thickener, defoamer, Water softener. Suitable water softener conclude a: polyphosphoric acid and a sodium, potassium or ammonium salt thereof; Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic triethylenetetramine, Hydroxyethylethylenediamintriacetic acid, nitrilotriacetic acid, 1,2-Diaminocyclohexantetraessigsäure and 1,3-diamino-2-propanol tetraacetic acid, and a sodium, potassium or ammonium salt thereof; Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxyethyne-1,1-diphosphonic acid, and a sodium, potassium or ammonium salt thereof.

The optimum amount of the one to use water softener varies depending from its chelating ability and the hardness and amount of hard water used. It moves in general in the range of 0.01 to 5% by weight and preferably from 0.01 to 0.5 % By weight based on the developer. The expected effect will not produced at low concentrations. At higher concentrations can adverse effects, such as a clear picture result.

The developer consists of the ones described above Components and water. It is advantageous for efficient transport, that the developer is a concentrate with a reduced water content is and can be diluted with water when used. The degree of concentration should be such that no component is separated or precipitated.

In addition to the above-mentioned developer, the developer described in JP-A-6-282079 is also usable in the present invention, which comprises: an alkali metal silicate having a SiO ₂ / M ₂ O (M is an alkali metal) molar ratio of 0.5 to 2 , 0 and a water-soluble ethylene oxide adduct obtained by adding 5 mol or more of ethylene oxide to a sugar alcohol having 4 or more hydroxy groups. The sugar alcohol is a polyhydric alcohol corresponding to a saccharide, and its aldehyde group and keto group have been reduced to a primary alcohol group and a secondary alcohol group, respectively. Specific examples of the sugar alcohols are D- or L-treitol, erythritol, D- or L-arabitol, ribitol, xylitol, D- or L-sorbitol, D- or L-mannitol, D- or L-iditol, D- or L- Talitol, dulcitol and allodulcitol. Condensed sugar alcohols such as di-, tri-, tetra-, penta- and hexaglycerol are also useful. The water-soluble ethylene oxide adduct is obtained by addition reaction of 5 moles or more of ethylene oxide per mole of sugar alcohol. If desired, propylene oxide may be block-copolymerized with the ethylene oxide adduct as long as the solubility is within a permissible range. The ethylene oxide adducts may be used either singly or in combination of two or more thereof.

The water-soluble ethylene oxide adduct becomes preferably in a concentration of 0.001 to 5 wt .-% and more preferably 0.001 to 2 wt .-% based on the developer added.

To accelerate the development, To disperse foam or increase the ink receptivity of the image area can this developer also various surfactants or organic solvents, as previously described.

[DEVELOPMENT AND POST-TREATMENT]

The PS plate, with the above described Developer was then subjected to post-treatment with wash water, a rinse solution containing a surfactant, etc. and a finishing or protective rubber solution mainly comprising Gum arabic, a starch derivative, etc. These post-treatments are appropriately combined.

In newer plate-making and Printing Industries will be an automatic processing machine for presensitized Plates (PS plate) widely used for rationalization and standardization used. The automatic processing machine is common divided into a development and a post-treatment part, each one a PS plate carrier unit, a processing tank and a spray unit, wherein each processing solution pumped and sprayed onto an exposed PS plate while it is being performed horizontally, to carry out development and after-treatment. A method in which a PS plate is passed through a processing tank filled with a processing solution, by means of submerged guide rollers and a method wherein a lower predetermined amount of water is added to a developed plate to perform washing, and the waste water is reused to the developer concentration to dilute, are recent known.

In such an automatic processing can the processing solutions with corresponding regeneration agents in accordance with the processing capacity and the Processing time of the processing solutions are regenerated. A disposable processing system for use in essentially unprocessed processing solution also applicable. The thus prepared lithographic printing plate is mounted on an offset printing machine to a large number to get prints.

As described above, the present invention, a positive-working photosensitive lithographic printing plate ready, which is outstanding in every way in terms of stain resistance while standing, press life, destruction properties, freedom on remaining color, printing properties and chemical resistance is. The positive-working photosensitive lithographic printing plate of the present invention shows these excellent properties even if the precursor of it containing no silicate Developer is developed.

The present invention will now be illustrated in more detail with reference to examples, but it should be noted that the present invention is by no means limited thereto. Unless otherwise indicated, all percentages and parts are in Weight indicated.

EXAMPLES 1 to 4 AND COMPARATIVE EXAMPLES 1 TO 5

The surface of a 0.24 mm thick aluminum plate (JIS A1050) was grained with a nylon brush and an aqueous slurry of 400 mesh pumice powder, followed by thorough washing with water. The aluminum plate was chemically etched by immersing in a 10% sodium hydroxide aqueous solution at 70 ° C for 60 seconds, followed by washing with running water. The plate surface was neutralized by washing with 20% aqueous nitric acid solution and washed with water. The surface of the aluminum plate was further electrolytically grained in a 1% nitric acid aqueous solution using a sinusoidal alternating current at V _A = 12.7 V and an anode electric quantity of 260 C / dm ² . The resulting surface had an average center-line roughness (Ra) of 0.55 μm. The plate was immersed in a 30% sulfuric acid aqueous solution for 2 minutes at 55 ° C for cleaning. Then, the plate was anodized in a 20% aqueous sulfuric acid solution at a current density of 14 A / dm ² to form 2.5 g / m ^{2 of} an anodized layer, followed by washing with water to prepare Substrate A.

Substrate A was mixed with a 2.5% aqueous Sodium silicate solution 10 seconds at 30 ° C treated and washed with water to obtain substrate B.

A solution of 0.3 g of the polymer shown in Table 1 below in a solvent mixture of 100 g of methanol and 1 g of water was applied to the surface of Substrate A or B to a dry coating weight of 15 mg / ^m2 and 15 seconds at 80 ° C dried to form an intermediate layer.

The photosensitive solution (A) having the following formulation was applied to the intermediate layer to a dry coating weight of 1.3 g / m ² and dried to form a photosensitive layer.

To the time required for the vacuum contact abbreviate, a layer of cheese was formed on the photosensitive layer, according to the in JP-B-61-28986, whereby photosensitive lithographic Printing plates were prepared (Examples 1 to 4).

For comparison, photosensitive lithographic printing plates were prepared in the same manner as described above except that photosensitive solution (A) was applied directly to Substrate A (Comparative Examples 1 and 2) or Substrate B (Comparative Example 3) or except that the polymer of the intermediate layer was coated β-alanine was replaced (Comparative Examples 4 and 5). FORMULATION OF THE LIGHT-SENSITIVE SOLUTION (A): Esters of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol acetone resin (the compound described in Example 1 of U.S. Pat US Pat. No. 3,635,709 ) 0.8 g Binder: Novolac I 1.5 g Novolak II 0.2 g Resin III unlike novolac 0.4 g pn-octylphenol-formaldehyde resin (the resin described in U.S. Pat US 4,123,279 ) 0.02 g Naphthoquinone-1,2-diazido-4-sulfonyl chloride 0.01 g tetrahydrophthalic 0.02 g benzoic acid 0.02 g pyrogallol 0.05 g 4- [pN, N-bis (ehtoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -S-triazine (hereinafter referred to as triazine A) 0.07 g Victoria Pure Blue BOH (counter anion: 1-naphthalene sulfonate, a product of Hodogaya Chemical Co., Ltd.) 0.045 g Fluorine-containing surfactant (F176PF, manufactured by Dainippon Ink & Chemicals, Inc.) 0.01 g methyl ethyl ketone 15 g 1-methoxy-2-propanol 10 g

Novolac (I)

Novolac (II)

Resin (III) other than novolac

Each photosensitive lithographic printing plate was imagewise exposed to light from a 2 kW metal halide The same was exposed to light at 1 m from the plate for 1 minute and with developer (A) or (B) having the following formulation at 30 ° C. for 12 seconds with a PS Processor 900 VR (manufactured by Fuji Photo Film Co., Ltd.). developed. FORMULATION OF THE DEVELOPER (A): D-sorbitol 5.1 parts sodium hydroxide 1.1 parts Triethanolamine ethylene oxide (30 mol) adduct 0.03 parts water 93.8 parts FORMULATION OF DEVELOPER (B): Aqueous silicate solution (SiO ₂ / Na ₂ O molar ratio: 1.2, SiO ₂ content: 1.4%) 100 parts Ethylenediaminethylene oxide (30 moles) adduct 0.03 parts

After the development processing, the unnecessary image area was destroyed with a destruction liquid (RP-2, manufactured by Fuji Photo Film Co., Ltd.) and washed with water. Destruction properties were determined by observing the indistinguishability of the destroyed area from the non-image area with the naked eye and evaluated as follows. AA ... No color difference is observed between the destroyed area and the non-image area. A ... A color difference is hardly observed between the destroyed area and the non-image area. B ... The destroyed area looks slightly darker than the non-image area. C ... The destroyed area looks obviously darker than the non-image area. D ... The destroyed area looks obviously dirtier than the non-image area.

Color remaining on the non-image area was determined by observing a density difference between the non-image area and the substrate before coating and evaluated as follows. AA ... No color difference is observed between the non-image area and the substrate before coating. A ... A color difference is hardly observed between the non-image area and the substrate before coating. B ... The non-image area looks slightly darker than the substrate before coating. C ... The non-image area obviously looks darker than the substrate before coating. D ... The non-image area looks significantly darker than the substrate before coating.

The durability of the printing plate to stain with ink on standing was determined as follows. Printing was performed on a printing machine (SOR-M, manufactured by Heidel) until 2,000 prints were obtained. The plate was removed from the printing press. After 60 minutes, printing was resumed and the prints generated were examined to see how the ink on the non-image area was removed. The result of the observation was evaluated as follows. A ... The ink on the non-image area is quickly removed. B ... It takes some time before the ink is removed on the non-image area. C ... It takes a long time before the ink on the non-image area is removed. D ... It takes a long time before the ink is removed on the non-image area.

To determine the properties The optical density of the photosensitive layer was before and after Exposure measured with a Macbeth densitometer to the difference the optical density (ΔD) to obtain. The bigger the Difference of the optical density achieved by exposure, the more the exposed area is clearer from the unexposed area distinguishable.

Chemical resistance of the printing plate was determined by the number of satisfactory prints using The printing plate can be made when printing on one Printing machine manufactured by Komori Insatsuki K.K. if the solid picture surface the plate with a plate cleaner (CL-2, manufactured by Fuji Photo Film Co., Ltd.) every 5,000 prints was wiped off. The bigger the Number of prints, the more satisfactory the chemical resistance.

Further, printing was among the same conditions as in the determination of chemical resistance but done without rubbing with a plate cleaner. The Number of prints obtained with satisfactory print quality taken as pressure life.

The results of these evaluations are shown in Table 1.

EXAMPLES 5 TO 10 AND COMPARATIVE EXAMPLES 6 TO 10

The surface of a 0.24 mm thick aluminum plate (JIS A1050) was grained with a nylon brush and an aqueous slurry of 400 mesh pumice powder, followed by thorough washing with water. The aluminum plate was chemically etched by immersing in a 10% sodium hydroxide aqueous solution at 70 ° C for 60 seconds, followed by washing with running water. The plate surface was neutralized by washing with 20% aqueous nitric acid solution and washed with water. The surface of the aluminum plate was further electrolytically grained in a 1% nitric acid aqueous solution using a sinusoidal alternating current at V _A = 12.7 V and an anode electric quantity of 260 C / dm ² . The resulting surface had an average center line roughness (Ra) of 0.55 μm. The plate was immersed in a 30% sulfuric acid aqueous solution for 2 minutes at 55 ° C for cleaning. Then, the plate was anodized in a sulfuric acid aqueous solution at a current density of 14 A / dm ² to form 2.5 g / m ^{2 of} an anodized layer, followed by washing with water to prepare Substrate A.

Substrate A was 0.001% aqueous Sodium silicate solution 10 seconds at 30 ° C treated and washed with water to produce substrate C.

A solution of 0.3 g of the polymer shown in Table 1 below in a solvent mixture of 90 g of methanol, 10 g of ethanol and 1 g of water was applied to substrate C to a dry coating weight of 15 mg / m ² and 15 seconds at 80 ° C dried to form an intermediate layer.

The photosensitive solution (B) having the following formulation was applied to the intermediate layer to a dry coating weight of 1.8 g / m ² and dried to form a photosensitive layer.

To the time required for the vacuum contact To shorten, a layer of cheese was formed on the photosensitive layer, according to the in JP-B-61-28986, whereby photosensitive lithographic Printing plates were prepared (Examples 5 to 8).

For comparison, photosensitive lithographic printing plates were prepared in the same manner as above except that photosensitive solution (B) was applied directly to Substrate A (Comparative Examples 6 and 7) or Substrate C (Comparative Example 8). Further, photosensitive lithographic printing plates were prepared in the same manner as described above except that substrate C or substrate A was used and the polymer of the intermediate layer was replaced by triethanolamine hydrochloride (Comparative Examples 9 and 10). FORMULATION OF THE LENS-SENSITIVE SOLUTION (B): Esters of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol acetone resin (the compound described in Example 1 of the US Pat. No. 3,635,709 ) 0.9 g Binder: Novolak IV 1.60 g Novolak V 0.3 g pn-octylphenol-formaldehyde resin (the resin described in U.S. Pat US 4,123,279 ) 0.02 g Naphthoquinone-1,2-diazido-4-sulfonyl chloride 0.01 g tetrahydrophthalic 0.02 g benzoic acid 0.02 g pyrogallol 0.05 g Triazine A 0.07 g Victoria Pure Blue BOH (counter anion: 1-naphthalene sulfonate, a product of Hodogaya Chemical Co., Ltd.) 0.10 g Fluorine-containing surfactant (F176PF, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06 g methyl ethyl ketone 12 g

Novel IV:

Novolak V:

Further, photosensitive lithographic printing plates were prepared in the same manner as in Examples 5 to 8 except that the polymer of the intermediate layer was replaced by the polymer shown in Table 1 and photosensitive solutions (C) having the following formulation were applied to the intermediate layer (Examples 9) and 10). FORMULATION OF THE LIGHT SENSITIVE SOLUTION (C): Esters of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 2,3,4-trihydroxybenzophenone (degree of esterification: 90%) 0.6 g N- (p-aminosulfonylphenyl) methacrylamide-acrylonitrile-methyl methacrylate copolymer (45/30/25 mole, Mw: 75,000) 1.7 g Novolak IV 0.7 g tetrahydrophthalic 0.05 g Triazine A 0.07 g Victoria Pure Blue BOH (counter anion: 1-naphthalene sulfonate, a product of Hodogaya Chemical Co., Ltd.) 0.05 g Fluorine-containing surfactant (F176PF, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06 g γ-butyrolactone 8.0 g methyl ethyl ketone 12.0 g 1-methoxy-2-propanol 10.0 g

Each of the resulting photosensitive Lithographic printing plates were imagewise in the same way as exposed in Example 1 and with developer (A) or (B) the same way as in Example 1 developed.

The developed plate was opened Destruction of properties, remaining paint, staining on standing, print outs, Press life and chemical resistance in the same way evaluated as in Example 1. The results obtained are in Table 1 shown.

COMPARATIVE EXAMPLE 11

A lithographic printing plate was in the same manner as in Example 1 except that comparative polymer 1 in the intermediate layer was used. The evaluated results are shown in Table 1.

COMPARATIVE POLYMER 1:

(Rf: 0.01 on alumina and 0.76 on silicon dioxide)

COMPARATIVE EXAMPLE 12

A lithographic printing plate was in the same manner as in Example 8, except that comparative polymer 2 was used in the intermediate layer. The evaluated results are shown in Table 1.

COMPARATIVE POLYMER 2:

(Rf: 0.07 on alumina and 0.80 on silicon dioxide)

COMPARATIVE EXAMPLE 13

A lithographic printing plate was prepared in the same manner as in Example 10 except that Comparative Polymer 3 was used in the intermediate layer. The evaluated results are shown in Table 1.

COMPARATIVE POLYMER 3:

(Rf: 0.075 on alumina and 0.52 on silica)

From the results in Table 1 shows that the inventive photosensitive lithographic Printing plate excellent in all aspects of stain resistance while standing, press life, destruction properties, freedom on remaining color, print properties and chemical resistance is.

While the invention in detail and with reference to specific examples it is obvious to one skilled in the art, that different changes and modifications can be made without the mind and scope deviate from it.

Claims (1)

A positive-working photosensitive lithographic printing plate comprising an aluminum substrate and a positive-working photosensitive layer, wherein the aluminum substrate is anodized and rendered water-wettable to form an aluminum oxide layer and a water-wettable layer on its surface, comprising an intermediate layer containing a polymer (A) a unit which interacts with the alumina layer which is a unit with an acid radical, and (B) a unit which interacts with the water-wettable layer which is a unit having an onium group, between the wettable layer and the photosensitive layer wherein the unit (B) is obtained from a monomer selected from the group consisting of the following formulas (III), (IV) and (V):

wherein J represents a divalent linking group; K represents an aromatic group or a substituted aromatic group; Each M is a divalent linking group; Y _{1 represents} an atom of Group V of the Periodic Table; Y _{2 represents} an atom of Group VI of the Periodic Table; Z ^{-1 represents} a counter anion; R _{2 represents} a hydrogen atom, an alkyl group or a halogen atom; R ₃ , R ₄ , R ₅ and R ₇ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted aralkyl group; R _{6 represents} an alkylidene group or a substituted alkylidene group; R ₃ and R ₄ or R ₆ and R ₇ may be taken together to form a ring; j, k and m are each 0 or 1; and u represents an integer of 1 to 3, wherein the photosensitive layer is formed of a photosensitive composition whose solubility or swellability is changed in the presence of a developing solution upon exposure to light, and wherein the polymer contained in the intermediate layer has an affinity for an alkaline Developer has what results in their removal from the substrate during the development process.